MgAl-LDH/CoFe2O4 and MgAl-CLDH/CoFe2O4 nanofibres were prepared by urea-hydrolysed hydrothermal reaction and the subsequent calcinations. The morphology and structure of the products were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscope and Fourier transformed infrared. The adsorption performance of MgAl-LDH/CoFe2O4 and MgAl-CLDH/CoFe2O4 nanofibres for the removal of an anionic dye (Congo Red, CR) from aqueous solution was investigated. The results showed that MgAl-LDH/CoFe2O4 and MgAl-CLDH/CoFe2O4 nanofibres are particularly efficient in removing CR. The adsorption follows a pseudo-second-order kinetic model and best fits the Langmuir isotherm model. The maximum adsorption capacities of MgAl-LDH/CoFe2O4 and MgAl-CLDH/CoFe2O4 nanofibres for CR were found to be 213.2 and 49.8 mg g−1, respectively. The both adsorption processes were found to be spontaneous and exothermic in nature.